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Research and Practice

Cite this: Chem. Educ. Res. Pract., 2012, 13, 69–79
www.rsc.org/cerp PERSPECTIVE
Green chemistry teaching in higher education: a review of effective
practicesw
John Andraos*a and Andrew P. Dicks*b
Received 13th September 2011, Accepted 12th January 2012
Published on 22 February 2012 on http://pubs.rsc.org | doi:10.1039/C1RP90065J
DOI: 10.1039/c1rp90065j
This account reviews published green chemistry teaching resources in print and online literature and
our experiences in teaching the subject to undergraduate students. Effective practices in lecture and
laboratory are highlighted and ongoing challenges are addressed, including areas in cutting edge green
chemistry research that impact its teaching in the undergraduate curriculum. In particular, the
influence of green chemistry on the overall teaching of organic chemistry is discussed.
Introduction until December 31st 2011, this amounted to an average of one

Downloaded on 01 October 2012
publication per monthly issue. The need for these resources is

As discussed recently (Anastas, 2011), the guiding theories and emphasized by comments from graduate students after attending
practices of green chemistry were first proposed twenty years ago the third annual American Chemical Society Green Chemistry
and have since become entrenched in the chemical literature. The Summer School (GCSS) in Montréal, Canada. It was noted that
seminal book on the subject was published some years later which ‘‘a common belief among the GCSS participants was that our
included a formulation of the Twelve Principles of Green Chemistry education would have been significantly enhanced with the
(Anastas and Warner, 1998). Subsequently, twelve more principles incorporation of green chemistry, beginning at the elementary
were suggested that are targeted at process chemists, chemical level and continuing throughout graduate course work’’ (Kitchens
engineers and chemical technologists (Winterton, 2001). Although et al., 2006). Other authors have reinforced the requirement of
this timeframe implies that it is still a relatively young area, several cultural change in chemical education, with statements such as
greener chemical approaches were adopted many decades before ‘‘academically, a green chemistry culture can be created through
the sustainability movement began. Some instances are highlighted higher expectations of sustainability taught via new curricula, and
in Table 1, and indicate, for example, that the notion of eliminating updated textbooks incorporating the 12 principles. This exemplifi-
reaction solvents or using alternatives such as water or ionic liquids cation must become a primary leadership goal predicated upon a
has a rich history. Table 1 additionally shows that a reaction belief in the long-term advantage of superior, evolutionary,
considered green from one perspective (solvent-free) can also be sustainable science’’ (Tucker, 2010).
viewed as decidedly ‘‘un-green’’ (using HgCl2 as a reagent) (Parker, Given the wealth of resources available, and the documented
1914). Nevertheless, these illustrations give credence to the claim importance of green chemistry education, this article reviews
that ‘‘new chemical techniques are unnecessary to achieve greener successful published instructional techniques in the field. It outlines
chemistry. Rather, it requires redirection of current techniques and the challenges faced in teaching green principles at the post-
capabilities within a new set of individual expectations’’ (Tucker, secondary level, focuses on advantageous approaches and con-
2010). cludes with a discussion of necessary improvements in green
As with any new area of scientific research, educators have teaching and research. The paper is written from the perspective
contemplated strategies to integrate green principles into of two North American teaching faculty members who have
undergraduate and graduate curricula. One early course fourteen years combined experience of teaching green chemistry
(‘‘Introduction to Green Chemistry’’) was offered at Carnegie to undergraduates from both lecture and laboratory perspectives.
Mellon University and described in the Journal of Chemical
Education (JCE) (Collins, 1995). This represented the first
pedagogical reference to green chemistry in JCE. Since that Challenges in teaching green chemistry
time, over 110 articles have appeared in JCE regarding an
1. Examples across the chemical sub-disciplines
aspect of green instruction (Fig. 1). From January 1st 2004
Most literature examples of green chemistry in the context of
a
Department of Chemistry, York University, Toronto, Ontario M3J 1P3, optimized syntheses are from an organic perspective. This
Canada. E-mail: c1000@careerchem.com includes pharmaceutically important target molecules such
b
Department of Chemistry, University of Toronto, Toronto, as sildenafil citrate (Viagrat) (Dunn et al., 2004; Dicks and
Ontario M5S 3H6, Canada. E-mail: adicks@chem.utoronto.ca
w This article is part of a themed issue on sustainable development and Batey, 2012; Edward, 2012) and ibuprofen (Advilt) (Cann
green chemistry in chemistry education. and Connelly, 2000). As such, the vast majority of green
This journal is c The Royal Society of Chemistry 2012 Chem. Educ. Res. Pract., 2012, 13, 69–79 69
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Table 1 Selected historical examples of greener chemical approaches
Greener approach Description Ref.

Solvent-free Disruption of silver chloride by mechanical force (mechanochemistry) Lea, 1892
transformations
Dry reaction between HgCl2 and KI upon grinding Parker, 1914
Synthesis of 2,4-dichlorophenoxyacetic acid (component of Agent Orange) Manske, 1949
Alternative Water as the solvent for urea synthesis from ammonium cyanate Wöhler, 1828
solvents
Formation and use of ionic liquids Walden, 1914; Calloway,
1935
Catalysis Vitamin B1 (thiamine) biocatalysis of condensation reactions Breslow, 1958
Organocatalysis of condensation reactions by amines Verley, 1899; Doebner, 1900;
Cope, 1937
Enzyme-catalyzed organic reactivity Warburg, 1906; Pottevin,
1906; Rosenthaler, 1908

Multi-component Preparation of dihydropyridines and dihydropyrimidones Hantzsch, 1882; Biginelli,
reactions 1893
Biofeedstocks Synthesis of furfural and levulinic acid (used to make 2-methyltetrahydrofuran, a greener Adams and Voorhees, 1921;
solvent) from corn cobs and cane sugar, respectively McKenzie, 1929
Sonochemistry Reaction rate enhancements by high frequency sound waves Richards and Loomis, 1927
Greener reagents Pyridinium tribromide as an alternative brominating agent to molecular Br2 Djerassi and Scholz, 1948
as a useful concept in the routine practice of tracking the

optimization of chemical reactions’’ (Calvo-Flores, 2009). In

some instances very similar approaches have been given subtly
different names by different authors, which can hinder the
teaching of fundamental green concepts. For example, the
terminologies ‘‘E-factor’’, ‘‘mass intensity’’, ‘‘mass productivity’’
and ‘‘process mass intensity’’ all refer to metrics highlighting the
amount of material used in a chemical process (Henderson et al.,
2010). A rationale has recently been proposed why process mass
intensity is the preferred metric choice in the pharmaceutical
industry (Jiménez-González et al., 2011). This has prompted an
Fig. 1 Annual number of publications dealing with green chemistry editorial policy change in the submission of papers to Organic
pedagogy (1995–2011, J. Chem. Educ.). Process Research and Development which must now include some
kind of metrics evaluation to assess the environmental impact
teaching resources have been developed in the field of organic and greenness of a chemical process or synthesis. Authors are
synthesis. However, the term ‘‘green chemistry’’ is not always also encouraged to follow green chemistry principles with respect
used by industrial process chemists in their published works, and to the choice of reaction solvent (Laird, 2012). Educators have an
there are historical examples of optimized syntheses that clearly increasingly challenging task in deciding which concepts to teach
fit the goals and description of the Twelve Principles. Some of and the specific literature to direct students towards. The use of
these methods go back a long way in the literature, and are well green metrics has been discussed from a teaching perspective
before any awareness of environmental impacts became fashion- (Andraos and Sayed, 2007; Ribeiro et al., 2010).
able (as described in the introduction to this article). There is a
growing need to expand the range of pedagogical materials from
3. Student textbook issues
other chemical subdisciplines (most notably within analytical/
environmental and physical chemistry), although some resources Green chemistry ideas and examples are generally presented as
do exist as outlined in Table 4. ‘‘optional material’’ (usually as side bars and vignettes) in
organic undergraduate textbooks (Smith, 2011; Vollhardt and
Schore, 2011; McMurry, 2012). Items included are typically
2. Primary literature metric issues
not part of the core material that students need to know (and
There has been much confusion over the terminology of green will not be tested on), and are largely described in a ‘‘show and
chemistry metrics during the last twenty years (Andraos, tell’’ manner. A related problem is that quantitative analysis of
2012(a)). A lack of metric standardization in the primary synthesis is seldom part of the chemical education students
research literature (and how each metric should be employed) receive. Textbooks routinely present a ‘‘yield is everything’’
has lead to significant misunderstandings. Indeed, ‘‘the field of mentality, with little or no reference to overall reaction
green metrics is plagued by authors’ continuous changing of efficiencies or identification of reaction by-products. At the
the names of the same ideas, which gives the impression that introductory level, discussions deal only with number of steps
there is yet a new metric to be defined, with a new insight. This and overall yield as the key parameters for synthesis
has been a serious liability towards the acceptance of this topic optimization.
70 Chem. Educ. Res. Pract., 2012, 13, 69–79 This journal is c The Royal Society of Chemistry 2012
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There are additional issues with how the subject of organic course, or to try and add greener modules to existing courses
chemistry is presented in some introductory textbooks. The across the curriculum? The pedagogical literature has shown
following is an outline of some important concerns: that either approach can be successful, but that there are
textbooks are often organized according to functional obvious ‘‘pros and cons’’ (Andraos, 2012(a)).
groups, not patterns of reactivity Launching a new offering with ‘‘green’’ in the title will
chemical transformations are rarely (if ever) balanced capture undergraduate interest given the current publicized
there are few citations to the original literature, so issues of sustainability and global environmental stewardship
students are forced to believe what the author says without (Marteel-Parrish, 2007). Ideas and concepts can be thoroughly
checking for themselves the validity of the claims made discussed and placed within the context of ‘‘real-world’’ case
examples are often not taken from the original literature, studies from the current chemical literature, leading to development
especially when discussing fundamental concepts such as of more advanced problems and assignments. Considering the
molecular structure and bonding extra time a dedicated course affords, students more clearly
there is a disconnect between concepts introduced and the appreciate that for problems posed in this field there is no single
originator(s) of the idea, and the circumstances around which ‘‘correct green answer’’, but rather there are a range of options that
the idea arose (the mechanics of how research is done is not need to be evaluated according to some criteria, and then a decision
shown to the student) is made as to which ‘‘answer’’ is best. A multivariate green exercise
there is an overwhelming emphasis on individual examples has recently been published where students consider nine life-cycle
(memorization) rather than on pattern recognition (understanding). assessment metrics in the context of an organic transformation
From a green chemistry perspective, there are also some (e.g. benzene to aniline) (Mercer et al., 2012). The instructor selects
textbook ‘‘myths’’ that impact the impressions students have several literature methods for each transformation with the student
about organic synthesis. These are listed below: goal of selecting the greenest route. In a similar vein at the
the terms ‘‘side product’’ and ‘‘by-product’’ are synonymous University of Porto, Portugal, students search for the greenest
convergent synthesis plans are always more material- metal-acetylacetonate synthesis experiment commonly included in
efficient than linear plans the teaching laboratory literature, and attempt to improve its
short synthesis plans are always more material-efficient greenness (Ribeiro and Machado, 2011). This idea of considering
than long plans multiple solutions and making decisions is typically a tremendous
the amount of catalyst used in a reaction (catalyst loading) departure from their previous chemistry learning experiences.
is much smaller than the substrate on which it acts. There is also a shift in how an instructor is to evaluate student
4. Curricular issues assignments based on this paradigm.
Integration of a green chemistry course is preferable with
Perhaps surprisingly, there are still relatively few undergraduate other non-science related courses in areas of business, ethics,
green chemistry courses in Canada that are available for students law and regulatory affairs, that have relevance in team-driven
to take (Andraos, 2012(a)). There are significantly more offerings in research strategies of the chemical industry. Conversely, a new
the United States, with one model published in JCE (Marteel- course is time-consuming to prepare and may not find room
Parrish, 2007), and another taught at Monash University, Australia within an already-crowded curriculum, especially if it is
(Raston and Scott, 2001). Such courses are invariably considered proposed as an elective. There will likely be a significant
electives, and are not mandatory to fulfill the requirements of an learning curve for the instructor(s) involved in delivering the
undergraduate chemistry major program. A common misconcep- course. Significant resistance may arise from research faculty
tion within academia is that green chemistry is a ‘‘soft’’ and who object to precious resources being spent in such a manner.
descriptive subject, with only rudimentary numerical analysis In comparison, the ‘‘greening’’ of existing courses has the
required (Amato, 1993). Quantitative reasoning is usually not advantage of being less time-consuming in terms of implemen-
considered a necessary skill in synthetic organic chemistry courses tation. Fewer resources are required in terms of administrative
at any undergraduate level. In fact, the essential skill of balancing costs. Students benefit from potentially seeing green principles
chemical equations is often not carried forward into organic from a variety of different perspectives in both lecture and
courses from first year general courses, yet this is compulsory laboratory venues, and new textbooks are unnecessary. However,
for the proper itemization and quantification of waste material green approaches will likely have to replace some more traditional
produced in chemical reactions. Toxicology, hazard analysis, content (which may be unpalatable), and material cannot be
safety, and waste minimization strategies are subjects not routinely covered at the same level of detail compared with a stand-alone
included in the core curriculum for the chemistry major degree. course. This strategy requires ‘‘buy-in’’ from a number of faculty
Finally, green chemistry is often mistaken as being synonymous members and instructors within a department, and ongoing close
with environmental chemistry amongst students and sometimes coordination between them.
even research faculty.
2. Primary literature ‘‘real-world’’ case studies

Effective teaching methods
The use of cutting-edge, up-to-the-minute case studies is an
1. Stand-alone course versus cross-curricular implementation
essential aspect of effective green chemistry teaching (Andraos,
An instructor planning to introduce green chemistry into an 2012(a)). These can be simply incorporated into either theoretical
undergraduate program is typically faced with the following or practical components of almost any course. An emphasis has
dilemma: is it better to design a brand-new, stand-alone previously been placed on highlighting the United States
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Presidential Green Chemistry Challenge Awards (Cann, 1999; discovery that green chemistry is all about decision making—by
Marteel-Parrish, 2007). These annual recognitions are in five its very nature, it is often an indefinite and ambiguous field. The
categories: the Greener Synthetic Pathways Award, the Greener final decision is a choice based on weighing favourable and
Reaction Conditions Award, the Designing Greener Chemicals unfavourable factors until an acceptable compromise is achieved,
Award, the Small Business Award and the Academic Award although the main goal is reaching certainty when a truly ‘‘green’’
(www.epa.gov/gcc/pubs/pgcc/award_categories.html). The project optimized plan is established (Mercer et al., 2012). The quest for
details of many awardees are suitable for inclusion in under- ‘‘greening’’ reactions is an iterative process that is never fully
graduate curricula, Table 2 lists three examples from the five 2011 reached. There is always room for improvement as new reactions
winners. Other instructive real-world organic teaching examples and methodologies are constantly being discovered. Important
have been described (Cann and Dickneider, 2004). Finding target molecules (such as the ones analyzed in the assignment
current green literature written at an appropriate level for instruc- described here) are always revisited for trying out new synthetic
tors and students at different academic levels to digest is straight- strategies. A corollary key concept is that the evaluation of
forward. Excellent journals include, but are not limited to Organic ‘‘greenness’’ is a relative comparison and not an absolute one.
Process Research and Development, ChemSusChem, Green This leads to the realization that if there is only one documented
Chemistry and Chemical & Engineering News (Table 2). Several synthesis plan available for a given target molecule then its
articles in Green Chemistry specifically deal with undergraduate ‘‘greenness’’ ranking cannot be determined formally, although
teaching methodologies (Matlack, 1999; Lennon et al., 2002; it may have some green attributes according to the Twelve
Tavener et al., 2003; Grant et al., 2004; Grant et al., 2005). Principles.
Many web-based green chemistry materials have additionally
been designed and published during the last decade. Table 3 4. Laboratory resources
illustrates a selected number of these to highlight the variety of
features available. There are on-line repositories of successful It is clear from peer-reviewed materials that a meaningful way
to teach and learn green chemistry is in a laboratory setting.
teaching modules (some submitted by authors worldwide), websites

to promote educator networking, metrics calculator programs and The first experiment published to appeal to organic instructors
papers from a virtual green chemistry teaching conference. was ‘‘an environmentally benign synthesis of adipic acid’’
A significant number of these resources were developed from the (Reed and Hutchison, 2000). Since that time, dedicated
primary literature, and more will undoubtedly appear as time organic laboratory textbooks have reached the market (Kirchhoff
progresses. and Ryan, 2002; Doxsee and Hutchison, 2004; Roesky and
Kennepohl, 2009). This literature provides detailed experimental
notes for students to follow and a green perspective on each
3. Quantitative problem set questions & decision-making
performed reaction. Reviews of undergraduate solvent-free
As stressed previously, a common perception of green chemistry reactions and aqueous organic transformations have also been
is that it is a qualitative discipline, rather than a quantitative one. compiled (Dicks, 2009(a), 2009(b)). More recently, a contributed
Contrary to this, it is critical that instructors move away from a textbook (‘‘Green Organic Chemistry in Lecture and Laboratory’’)
‘‘show and tell’’ approach to a decision-making approach which seeks to summarize major developments made in the field during
is based on numerical data. A written assignment has been the last decade (Dicks, 2012). Surprisingly, however, a recent
included in an upper-level green chemistry course that requires survey of over 130 undergraduate organic chemistry laboratories
undergraduates to critique several synthesis plans towards a in the United States showed that although waste reduction was a
‘‘real-world’’ molecule (e.g. a cosmetic or a dyestuff), using significant consideration, green practical techniques were deemed
sustainability principles (Andraos, 2012(a)). Students indepen- relatively unimportant (Martin et al., 2011).
dently select a target compound themselves from a list and their From these published textbooks, one may begin to
work is evaluated in terms of both content and presentation. It is think that green principles only impact organic chemists.
noteworthy that one undergraduate report from this assignment However, book chapters have been written on (i) teaching
has been published in a peer-reviewed journal (Andraos and green analytical chemistry with laboratory examples (Gron,
Izhakova, 2006). Adopting this approach leads to student 2009) and (ii) incorporating environmental issues into
Table 2 Recent case studies suitable for undergraduate curricula
Journal/resource title Recent case study Ref.

US Presidential Green Chemistry Challenge Surfactant for transition metal catalysis of organic reactions in water Ritter, 2011(a)
Awards
Halogen-free copolymer membranes for water purification Ritter, 2011(b)
Cost-effective microbial fermentation route to 1,4-butanediol Ritter, 2011(c)
Organic Process Research and Development Enzyme-mediated preparation of Lyrica Martinez et al., 2008
Solvent-free and chemoselective carboxylic acid esterifications Rekha et al., 2009
ChemSusChem Direct surfactant synthesis using dodecylbenzenesulfonic acid catalyst Gaudin et al., 2011
Flow microreactors for industrial scale processes Yoshida et al., 2011
Green Chemistry Isolation of orange oil components using distillation from ionic liquid Bica et al., 2011
Perkin reaction in ionic liquid solvent Pawar et al., 2011
Chemical & Engineering News Phasing out manufacture of a flame retardant (decabromodiphenyl ether) Hess, 2010
Production of hardened building materials with low energy demands Voith, 2010
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Table 3 Selected web-based green chemistry teaching resources
Resource Organizing institution Description

Greener Education Materials for Chemists (GEMs) University of Oregon, USA searchable database to sort teaching resources (theoretical
and practical) by academic level and desirable green
principles (Haack et al., 2005)
NOP (‘‘Nachhaltigkeit im Organisch-chemischen Universität Regensburg, collection of laboratory experiments used to incorporate
Praktikum’’): Sustainability in the Organic Germany sustainability and green chemistry into undergraduate
Chemistry Laboratory Course courses (Ranke et al., 2008)
Green Chemistry Resource Exchange American Chemical Society archive of materials concerning green chemistry and related
Green Chemistry Institute novel technologies
Green Chemistry Education Network (GCEdNet) University of Oregon, USA educator network to facilitate sharing of greener teaching
strategies
Green Chemistry Assistant St. Olaf College, Minnesota, calculator to determine green parameters (e.g. theoretical
USA atom economy) for a reaction of interest
The Ecoscale EcoSynth, Oostende, Belgium post-synthesis tool to evaluate ‘‘greenness’’ of an organic
reaction (Van Aken et al., 2006)
Educating the Next Generation: Green and American Chemical Society on-line green chemical education conference; seven
Sustainable Chemistry Committee on Computers in academic papers presented during April–June 2010
Chemical Education
inorganic chemistry (Huheey, 1996). A search of the recent organic reactions, having often heard the opposite during
pedagogical literature identifies a number of appropriate lecture classes. After learning about ‘‘traditional’’ textbook
experiments in ‘‘non-organic’’ areas (Table 4), illustrating reaction solvents such as dichloromethane and acetonitrile,
the cross-curricular impact of green chemistry. More work they embrace performing reactions under solventless condi-
is needed in these venues to develop a comprehensive suite tions. A novel green laboratory teaching approach has been
of practical resources that facilitates implementation within adopted where data generation and interpretation leads to
larger and smaller courses. The journal Green Chemistry has development of a principle statement (Teixeira et al., 2010).
additionally published educational efforts from a laboratory Students are guided to devise a more sustainable solvent
perspective (Warner et al., 2001; Houri and Wehbe, 2003; system for Grignard reactivity based upon their own acquired
McKenzie et al., 2004). data and that provided to them. A one-term, integrated
Direct application of the founding Twelve Principles in a project for the undergraduate organic laboratory involves
practical environment is now so straightforward that it makes synthesis of Nylon 6,6 from cyclohexanol (Dintzner et al.,
little sense for educators to avoid ‘‘greening’’ their experi- 2012). The product of one reaction is used as a starting
ments. Most contemporary students have a heightened sense material for the following one in an effort to minimize waste,
of environmental responsibility, and consider it important to and students are exposed to several other green principles in
be taught about modern approaches towards laboratory sus- the context of a familiar target compound.
tainability (Kitchens et al., 2006). They are, for example, A third-year undergraduate catalytic chemistry course
initially surprised that water is an excellent solvent for many (‘‘Organic Synthesis Techniques’’) has been designed at the
Table 4 Greener undergraduate laboratory experiments in ‘‘non-organic’’ areas
Field/sub-
discipline Experiment description Ref.
Introductory/ Colligative properties of fatty acids McCarthy and Gordon-Wylie, 2005; Iacobucci
General et al., 2006
Stoichiometry: composition of a sodium carbonate/sodium bicarbonate mixture Cacciatore and Sevian, 2006
Nanoparticle synthesis using a plant leaf extract Richardson et al., 2006
Solubility, equilibrium, and periodicity concepts surrounding Group II Cacciatore et al., 2008
hydroxides
Calculating the formula of copper(II) chloride dihydrate Klingshirn et al., 2008
Superconductor synthesis: the Meissner effect She and Liu, 2008
Analytical Spectrophotometric measurement of creatinine in urine Correia et al., 2004
Measurement of mercury in cow and goat milk by atomic fluorescence Armenta and de la Guardia, 2011
Electrochemical cell for cyclic voltammetry Olson and Buhlmann, 2010
Biological Purification of Escherichia coli DNA using laundry detergent Sims et al., 2010
Environmental Extraction of metal contaminants from environmental samples with micelles Giokas et al., 2003
Inorganic Preparation of tetraamido-N Cu(III) and Co(III) complexes Uffelman et al., 2004(a), 2004(b)
Cation qualitative analysis via spot tests Sidhwani and Chowdhury, 2008
Synthesis of Group II metal oxalate hydrates Canal, 2009
Metalloporphyrins as oxidation catalysts Clark et al., 2012
Solvent-free synthesis of Cu(II) phthalocyanine Sharma et al., 2011
Materials Alkanethiol monolayer formation on gold films McKenzie et al., 2004
Physical Synthesis and analysis of quantum dot nanocrystals Boatman et al., 2005
Properties of biodiesel: heat of combustion, density and cloudpoint Akers et al., 2006
Energy content and viscosity of biofuels Wagner et al., 2010
Density measurements using a Galilean thermometer Priest et al., 2011
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Table 5 Green reactivity features in Organic Synthesis Techniques
Reaction Catalytic approach Additional green features Ref.

Williamson ether synthesis phase-transfer catalysis aqueous reactivity Vanden Eynde and
Mailleux, 2001
Verley-Doebner condensation organocatalysis — Stabile and Dicks, 2003
Biginelli reaction Brønsted acid catalysis high atom economy, reduction in solvent usage Aktoudianakis et al., 2009
Biginelli reaction Lewis acid catalysis high atom economy, solvent-free reactivity, Aktoudianakis et al., 2009
reduced energy requirements
Primary alcohol oxidation transition metal catalysis (Ru(VII)) mild conditions, short reaction time Koroluk et al., 2011
Suzuki reaction transition metal catalysis (Pd) aqueous reactivity & purification solvent Aktoudianakis et al., 2008
Heck reaction transition metal catalysis (Pd(II)) aqueous reactivity & purification solvent Cheung et al., 2007
University of Toronto where green chemistry is a thread the experiment?’’; (ii) ‘‘what was not green?’’; (iii) ‘‘how could the
running through both lecture and laboratory components experiment be made greener?’’. It is certainly the case that ‘‘all
(Dicks and Batey, 2012). A number of novel pedagogical that glitters is not green’’ in the chemical research literature—a
experiments featuring catalysis are incorporated and listed in point elaborated on in the ‘‘inaccurate assertions of ‘‘greenness’’’’
Table 5, along with additional green aspects of each reaction. section concluding this article.
For each system, students undertake metric analysis (calcu-
lation of experimental atom economies and waste production). 6. Retooling introductory general and organic courses
This becomes especially instructive when ‘‘traditional’’ and In order to facilitate the introduction of either a new green
‘‘modern’’ approaches towards the same Biginelli reaction chemistry course or separate units into a number of different
are employed (Aktoudianakis et al., 2009). The traditional offerings, some important curricular issues should be
Biginelli reaction involves heating an aromatic aldehyde, ethyl addressed. Firstly, it is ideal if the instructor charged with
acetoacetate and urea with mineral acid catalyst in ethanol designing and implementing a green course is the same one
solvent for 90 min to form a dihydropyrimidone. In compari- who teaches at least one introductory prerequisite course.
son, the modern solventless method utilizes ZnCl2 as the A need exists to integrate important principles into first-year
catalyst, reducing the heating time to 20 min. This addresses general chemistry courses, particularly dealing with stoichio-
two of the Twelve Principles: ‘‘use of auxiliary substances metry discussions. An attempt to achieve this in the context of
should be made unnecessary wherever possible’’ and ‘‘energy some introductory exercises has been published (Song et al.,
requirements of chemical processes should be recognized and 2004). Also, both lectures and laboratories associated with
should be minimized’’ (Anastas and Warner, 1998). Each such courses are ideal for discussing the principles of process
student performs both procedures within one laboratory atom economy and E-factor. Secondly, there are specific items
session so that quantitative comparison between the reactions in introductory organic chemistry courses (typically taught in
is straightforward. second-year) that require revision and/or amendment. These
The impact of being trained to critically evaluate transfor- include the following major points:
mations from a green perspective is apparent towards the end how to consistently balance chemical equations, indicating
of Organic Synthesis Techniques. Each class member is the presence of all organic and inorganic products
assigned an individualized target compound to synthesize in how to clearly represent organic molecules on paper/using
two laboratory periods from a given starting material. They chemical drawing software, keeping the same structural aspect
are encouraged to generally employ green chemistry principles, throughout a synthetic pathway
adopting catalytic measures where possible. Students are respon- how to locate the starting materials of a chemical synthesis
sible for all aspects of planning and synthesis execution in the desired product structure
and routinely incorporate a number of sustainable strategies making it known to students from the outset the complete
(e.g. using solvents derived from biomass and greener reagents, classification of organic reaction types: substitutions, rearrange-
solvent-free reactivity, reactions under mild conditions) (Dicks ments, redox reactions, additions (includes couplings, multi-compo-
and Batey, 2012). nent reactions, cyclizations, condensations), and eliminations
how to identify nucleophilic/electrophilic sites in any kind
5. Different ‘‘shades of green’’ of chemical structure
The term ‘‘shades of green’’ has been applied to describe the how to identify BrØnsted-type and Lewis-type acidic/basic
variable environmental friendliness of different reaction solvents sites in any kind of chemical structure
(Clark and Tavener, 2007). This is instructive terminology to establishing connections between correctly balancing an
share with undergraduates, who are much more familiar (and equation, pinpointing starting materials in the target product
comfortable) with a ‘‘correct’’ answer to a chemical problem. It structure and constructing a reasonable curved arrow mechanism
should be emphasized that applying green chemistry principles to for every new reaction taught.
a system is a comparative exercise and not an absolute one, and
that it is not ‘‘all or nothing’’ (Kerr and Brown, 2009; Bennett,
Payoffs of green chemistry thinking
2010). An asymptotic approach has been outlined where students
consider the following three questions after performing any There are major advantages afforded to undergraduates by
laboratory work (Goodwin, 2004): (i) ‘‘what was green about inclusion of green principles into their educational experience.
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As most materials have been developed for organic courses, trends. As mentioned earlier, there are many false claims of
three important skills typically acquired from them are ‘‘greenness’’ in the chemical literature. Often an argument is
outlined below with specific examples. made on the basis of only one of the Twelve Principles. This
Deeper analysis and richer discussion of synthesis perfor- represents a narrow view rather than a multivariate global
mances by comparative analysis. In a third-year undergraduate approach which considers all material and energy consump-
Industrial and Green Chemistry course, students analyze multiple tion, and the environmental impact of any waste produced. An
synthesis plans towards three synthetic targets: ibuprofen, prava- example here is the oft-quoted declaration of a ‘‘solventless’’
doline and a dihydrodiazepine (Andraos, 2012(a)). Each synthesis reaction. In the vast majority of cases, this only applies to no
plan is taken from the primary chemical literature. Each example reaction solvent being used—it does not include or take into
illustrates the ubiquitous problem that, for most of the time, no account any solvents used in product work-up or purification
one plan has all the ‘‘right’’ fully optimized characteristics in every operations (Dicks, 2009(a)). A ‘‘dry-laboratory’’ teaching
category. By exposing students to such well-documented real- approach has been reported where students focus on the
world scenarios they begin to appreciate the difficulties involved in impact of auxiliary substances such as extraction solvents
reaction optimization. They become able to directly link that and separation agents as sources of waste after a solvent-free
the endeavours of optimization and ‘‘greening’’ are one and the organic transformation (Van Arnum, 2005).
same – a point emphasized by Laird’s editorial (Laird, 2012). They In a similar fashion, just because a reaction is run in water or
also discover that because chemistry is an experimental science in an ionic liquid does not make it inevitably ‘‘green’’, and simply
governed by compromise, optimization inevitably involves prioriti- because a reaction begins with a biofeedstock does not make it
zation of variables. They additionally learn that metrics are automatically ‘‘sustainable’’. Interestingly, the journal Green
important tools to verify claims of greenness made in the literature Chemistry has revised its editorial policy on accepting papers
and to proofread experimental procedures. for publication on the subject of ionic liquids precisely because of
Critical evaluation of merits and bottlenecks in synthesis false advertisements of ionic liquids as ‘‘green solvents’’ (Welton,
plans, consequently offering creative solutions that can address the 2011). Multi-component reactions (MCRs) and ‘‘one-pot’’
shortcomings. In the same course, students undertake innovative reactions are not necessarily ‘‘green’’—even though they gener-
problem set questions covering various aspects of synthesis ally proceed with high atom economy, they may require toxic
optimization. These include reaction network analysis, cost ana- reagents/solvents or chromatographic separation of products.
lysis, energy input analysis, comparison of linear, convergent, and A similar situation exists for reactions performed under catalytic
divergent strategies, green metrics analysis for material efficiency conditions. The tetrapropylammonium perruthenate (TPAP)
and probability analysis based on target thresholds for reaction catalysis of primary alcohol oxidation to an aldehyde has been
‘‘greenness’’. They suggest multiple synthesis plans for a single undertaken and analyzed by undergraduates within the context
target molecule given various constraints simulating real-world of the Twelve Principles (Koroluk et al., 2011). Student laboratory
situations, including availability of source starting materials and reports reflect the understanding that simply because a reaction
threshold limits on atom economies for reactions and the overall employs a catalyst, it is not automatically a perfectly green
proposed synthesis plans (Andraos, 2012(a)). process. A recent statistical survey of over 1400 such reactions
Increased memory retention of fundamental concepts published up to 2010 as part of a larger evaluation of a synthesis
learned, particularly if real-world industrial chemistry examples database showed that 54% of them would satisfy simultaneously
are discussed. A nice illustrative example is the three industrial the basic criteria of kernel reaction mass efficiencies (excluding all
syntheses of beta-carotene, a food colourant, which highlights the solvents and auxiliary materials) exceeding 60% and reaction
discovery and application of three fundamental organic reactions yields exceeding 80% (Andraos, 2011(b)). These kinds of reality
that students learn about in introductory organic chemistry checks compel educators to ensure that students learn to adopt a
courses: the Wittig reaction (BASF synthesis) (Nuerrenbach balanced modus operandi when assessing ‘‘greenness’’.
et al., 1977), the hydrogenation of alkynes to cis-olefins using
2. Attention to experimental detail
Lindlar’s catalyst (Hoffmann-LaRoche synthesis) (Isler et al.,
1947; Inhoffen et al., 1950; Isler et al., 1956; Surmatis and Ofner, The itemization of experimental procedural details needs to
1961), and the McMurry coupling of ketones to olefins (McMurry dramatically improve in journal articles and patents, if any
and Fleming, 1974). Telling students the background story behind reliable estimates of waste production analysis are to be made.
the discovery of these reactions not only helps them remember the There is often casual reporting of quantities of materials used
reactions, but also illustrates the circumstances, motivation, and in work-up and purification procedures (e.g. volumes of all
mechanics of how real research is done in an industrial setting. extraction solvents, volumes of chromatographic packing
materials, volumes of elution solvents, masses of drying
agents, masses of gaseous reagents). Reaction yields may not
Conclusions—areas for improvement in teaching and be quoted or may be incorrectly calculated. The frequency of
research revealing reaction performance in patents is lower than in
journal articles, which impacts on the metrics evaluation of
1. Inaccurate assertions of ‘‘greenness’’
good industrial examples taken from the patent literature to
A symbiotic relationship exists between research and teaching illustrate green chemistry ideas. Evaluation of plans and
aspects of any academic discipline. The next generation of reactions should include the synthesis of ionic liquid solvents
researchers ‘‘learn their trade’’ in the undergraduate classroom and specialized catalysts or ligands, as these are routinely
and modern teaching practices are shaped by current research omitted from the main synthesis evaluation. Often the structure
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of a specialized catalyst involves a more complicated synthesis and is also the medium of choice for work-up washes, it is not
than the target product that the catalyst is designed to help universally included in cost calculations of input materials in a
generate. This lack of detail severely hampers the decision- synthesis plan. Research into increasing its use as a reaction
making process between the relative ‘‘greenness’’ of two or more solvent for a wide variety of organic reactions is gaining
synthetic routes. Biocatalytic transformations are generally traction in the undergraduate laboratory curriculum (Dicks,
poorly documented in terms of the needs of a chemist to evaluate 2009(b); Sauer, 2012). Widespread success in these and associated
reaction performance. Reaction yields are often reported as fields may lead to a re-writing of undergraduate textbooks as a
molar yields with respect to the substrate of interest, which paradigm shift evolves (Tucker, 2010). The emerging field of
may or may not be the limiting reagent. Stoichiometrically continuous flow reactors to carry out reactions instead of tradi-
balanced equations may not be possible to write down for such tional round-bottomed flasks promises to revolutionize the scope
reactions since the chemistries of the transformations may not be of reaction possibilities including control of thermodynamic and
fully known. kinetic products by changing flow rates of reagents (Ley and
Baxendale, 2002(a), 2002(b); Ley and Baxendale, 2008; Wiles

3. Energy and environmental considerations and Watts, 2008; Yoshida et al., 2008; Yoshida, 2010; Glasnov
and Kappe, 2011; Yoshida et al., 2011). However, there has
The assessment of energy consumption is not routinely disclosed
not yet been any demonstration of this technique in an under-
as part of the standard protocol in reporting experimental
graduate laboratory setting, nor has there been any reported
procedures. This becomes particularly problematic for proper
substantive evidence of reduction in solvent demand by metrics
evaluation of microwave-based chemical transformations against
evaluation. Finally, as mentioned previously, quantification of
traditional heating methods since these are often quoted as
energy consumption and costs for chemical reactions has
greener than conventional procedures, with little convincing hard
received little attention from both research and teaching perspec-
evidence. Often papers quote some fragmented combination of
tives (Gronnow et al., 2005).
power consumption in watts, reaction time, or temperature of
reaction without accounting for the intrinsic efficiency of the

microwave apparatus used. This state of affairs makes it difficult Summary
to determine the actual energy consumption. The commonly-
held belief that these kinds of reactions are energy efficient has In this paper we have reviewed approaches towards green
been recently challenged (Razzaq and Kappe, 2008). Addition- chemistry education with the aim of highlighting effective
ally, reliable environmental impact metrics data (which are instructional strategies as well as ongoing challenges. As
important for life cycle analysis) are often difficult to find since instructors in this exciting field we have gained greater personal
they may be scattered widely in the literature, or are found in satisfaction in teaching and appreciation for the subject of
unfamiliar sources to most chemists. This impacts the incorpor- chemistry. Particularly satisfying from this work is the accom-
ation of such metrics in the evaluation of synthesis routes beyond plishments we have seen in the students we have had the privilege
material consumption. An attempt has been made to rectify this to teach over the last decade. It is clear that much work remains to
situation in the context of a holistic problems-based assignment be done to incorporate green chemistry into the accepted main-
for undergraduate students in a combined third-year green and stream education of future chemists. We hope that instructors
environmental chemistry course taught at Queen’s University, reading this account will be inspired to join this worthy enterprise.
Canada (Mercer et al., 2012).
Notes and references
4. Pedagogical gaps
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View Online / Journal Homepage / Table of Contents for this issue

Chemistry Education Dynamic Article Links

Research and Practice

Introduction until December 31st 2011, this amounted to an average of one

publication per monthly issue. The need for these resources is

Table 1 Selected historical examples of greener chemical approaches

Greener approach Description Ref.

1906; Rosenthaler, 1908

as a useful concept in the routine practice of tracking the

optimization of chemical reactions’’ (Calvo-Flores, 2009). In

2. Primary literature ‘‘real-world’’ case studies

teaching modules (some submitted by authors worldwide), websites

Table 2 Recent case studies suitable for undergraduate curricula

Journal/resource title Recent case study Ref.

Table 3 Selected web-based green chemistry teaching resources

Resource Organizing institution Description

Table 4 Greener undergraduate laboratory experiments in ‘‘non-organic’’ areas

Table 5 Green reactivity features in Organic Synthesis Techniques

Reaction Catalytic approach Additional green features Ref.

Baxendale, 2002(a), 2002(b); Ley and Baxendale, 2008; Wiles

reaction without accounting for the intrinsic eﬃciency of the

13, 1997–1999. an environmentally benign synthesis of sildenaﬁl citrate (Viagrat)

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